Waterinsoluble azodyestuff



Patented Dec. 19, 1933 r s I UNITED STATES PATENT OFFICE WATERINSOLUBLE AZODYESTUFF Friedrich Muth, Leverkusen-I. G., Werk, Germany, assignor to General Aniline Works, Inc., New York, N, IL, a corporation of Delaware 7 No Drawing. Application April 4, 1932, Serial No. 603,207, and in Germany April 18, 1931 @4 Claims. (Cl. 260-86) The present invention relates tov waterinsolucellulosic fibre. Dyestuffs of various shades are ble azodyestufls, more particularly .it relates to thus obtained, which when produced on the fibre dyestufis which maybe represented by the probaccording to the known method of producing ice able general formula: colors, show goodfastness properties. 7 i a i The hydroxycarbazole carboxylic acid arylam- 55 ides used as coupling components in the manufacture of my dyestuffs have been described and claimed in my co-pending application Serial No.

7 603,208, filed April 4, 1.932 entitled Newhy- N=N R droxycarbazole carboxylic acid arylamides. 6o

, a The invention is illustrated by the following exwherein R stands for the radical of a diazotized amples' but is not restricted thereto: primary amine suitable for producing an azodye- Example TP st fi c as fo a-mdicaliof an aminobenzene, carbazole-iZ-carboxylic acid-,p-chloranilide (obamino-naphthalene, aminocarbaz'ole, aminoantamed after w te i t o P pyridine in 5 thmquinone, aminofluorenonef stands for small needles of the meltmgpomt 276 C.) are 7 alkyl or for a hydrocarbon radical of the aromatic dlssolved in 5 times the quantltY of h or aromatic-aliphaticseries and R stands for the quantity, of water P tunes the quam'fllty an aromatic or heterocyolic nucleus, for examof a aqueous s? The 11m 20 ple, for a benzene, naphthalene,.indole, carbazole, is introduced into 1000 htre Water collbammg diphenyleneoxide, fiuorene or fiuorenone nuclebesiqes caustic Soda lye protectwe collold 4 us, and wherein all nuclei maybe substituted wettmgfigentg V by one or more monovalent: substituents, such thls solutmn 50 g of cotton are lmpreg' as halogen, the mtro group an alkyl group, an nated for half an hour, squeezed oil? and developed alkoxy group, an aryloxyigroup and an acylamino m a bath containing 1.65 kgs. of diazotized ingroup, but with the exception of a'group inducing m Aftefr hajlf an hour w cotton 15 solubility in water, such as the sulfonic acid rlnsed, soapeq whlle sun hot and dned- A deep group, the carboirvlic acid group or a further brown obtamedhydmxygmun I In an analogous manner the following shades My dyestuffs are obtainable according to known can be obtmned: I g

methods by diazotizing in the usual manner any D1310 a i v a primary amine suitable for producing an azot m A reddisbbmwn dy fi d Coupling with hydroxycalbazole 6-chloro-2-toluidine- A reddish-deep brown carboxylic acid arylamide of the general formula: 5 n t 2 di A th u m-amino-azotoluene of the formula:

O O NH RII CH] N on NH: l 40 1 A deep brown.

v wherein the figures R' and R" means the same as stated above, thereby the components 7 33H: being selected in such a manner that apart from V V I 45 the hydroxy group present in the coupling com- 1 amino-4-benzoylamino ponent none contains a group inducing solubility 2.5-diethoxybenzene A clear bluish violet in water. A y 5- nitro+3-toluidine Reddish-brown The coupling can be performed in substance, 4-amino-2-.5-dimethoxy-4- on a substratum or on the fibre, especially the .'nitro-Ll'-azobenzene Reddish-blue-black 10o From -the 9-methyl-2-hydroxycarbazole-3-carboxylic acid-o-anisidide the following shades can be obtained:

Diazo bath from:

3-chloraniline A yellowish deep brown 3-nitraniline A deep brown l-methyl 2 amino-4- chlorobenzene A reddish-brown o-aminoazotoluene of the formula:

CH3 A violet-brown.

-amino 2.5 dimethoxy-4-nitro 1.1-azobenzene A dark blue From the 9 ethyl-2-hydroxycarbazole 3-carboxylic acid-o-toluidide (obtained after recrystallization from toluene in the form of cubes oi; the

melting point 187 C.) the following shades can be obtained:

Diazo bath from:

3-chloraniline A yellowish dark brown 2.5, -dichloraniline A deep brown 4-nitraniline- A reddish-brown 1'.-- methyl-2-amino. 4:- r V chlorobenzene A yellowish dark brown 1 amino -2.5.r-diethoxy- V zene A violet F 95 1 the;9 m hy r rhydr x fl azolwr a boxylic acid-anilide the following shades can be b ain d; 7 I

D Q bath .from:

2,5-dichloraniline Adeep b rown 1 methyl z-aminofi-chloro benzenenfl A deep brown benzene Acorinth 1 am no-2 -di tnQx r e zoylaminobenzene'"; A violet 1 .m ih :am ino-: hlom benzeneu u; A reddish-brown From the 9 -methyl-s2-hydroxycarbazolee3-carboxylic. acid'o-toluidide (obtained after recrystale lization from: toluenein the. form of yellow sticks. of the melting point 193 C.) the followingishades canibe obtained:

Diazo bath from:

3-nitraniline A dark yellowish-brown 4-nitraniline A dark red dish-brown Similar but deeper shades are -Vobtained when substituting in the above combinations the 9- methyl-2-hydroxycarbazole-3-carboxyl-ic acid-otoluidide by the 9-methyl-2-hydroxycarbazole-3- carboxylic acid-a-naphthylamide.

Example 2.--3.4 grams of .2-aminocarbazole are diazotized in the usual manner with sodium nitrite in hydrochloric acid solu tion. The diazo solution is introduced into a solution of d grams of 9-methyl-2-hydroxycarbazole carboxylic acid-2'- methoxyanilide, said solution having been prepared by dissolving the arylamide with the aid of 1.5 grams of caustic sodain 150 ccs'. ofwater By the addition. o-sodium-.bicarbonate the solution of the two components isreridered sodaalka line and coupling is performed with the addition oi an excess. of sodium bicarbonate and 101 lice.

The dyestufi formed is filtered with suction and dried. It is a brown powder. The dyestufi has the following formula:

By substituting the 2-aminocarbazole by the z-aininodiphenylenoxide there is obtained a dyestuff of the following formula:

I I I Hat scribed in Example 2; After filteringiand dryinz, 15

the dyestuif of the formula:

is obtained in form of a brown powder.

The dyestufi of the formula;

OCH:

N01 has similam-propertiea- When producing these dyestuffs on the flbre violet shades of- 1 good fastnessproperties-are obtained IcIaimz 1. Azodyestufls of the probable general formula:

OO NHR" OH N 11' N=NB wherein R stands for the radical of a diazotized primary aromatic amine suitable for producing an azodyestufl, R' stands for alkyl or for an aromatic radical of the benzeneor naphthaleneof the probable general 00NHR" on I wherein R and R" benzene or naphthalene stand for nuclei of the series and R' stands for alkyl, and wherein the nuclei may be substituted by substituents selected from the group consisting of halogen, the nitro group, an alkyl group,

an alkoxy. group, an aryloxy group and an acylamino group, yielding, when produced on the fibre, various shades of good fastness properties.

3, Azodyestufi's of the probable general formula:

(JO-NH-R" on N it N=N-R wherein R and R" stand for benzene nuclei which may be substituted by substituents selected from the group consisting of halogen, the nitro group an alkyl group, an alkoxy group, an aryloxy group and an acylamino group, and R' stands for methyl or ethyl, yielding, when produced on the fibre, generally violet to brown shades of good fastness properties. 4. The azodyestufi of the following formula:

0 0-NHO01 yielding, when produced on, the fibre, brown shades of good fastness properties.

FRIEDRICH MU'I'H. 

